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WikiJournal of , 2018, 1(2):7 doi: 10.15347/wjs/2018.007 Encyclopedic Review Article

Lead: properties, history, and applications Mikhail Boldyrev¹*, et al.

Abstract is a with the 82 and the symbol Pb (from the plumbum). It is a heavy that is denser than most common materials. Lead is soft and malleable, and has a relatively low . When freshly cut, lead is silvery with a hint of blue; it to a dull gray color when exposed to air. Lead has the highest atomic number of any stable element and concludes three major decay chains of heavier elements. Lead is a relatively unreactive post-. Its weak metallic character is illustrated by its amphoteric ; lead and its react with and bases, and it tends to form covalent bonds. Compounds of lead are usually found in the +2 rather than the +4 state common with lighter members of the . Exceptions are mostly limited to organolead compounds. Like the lighter members of the group, lead tends to bond with itself; it can form chains, rings and polyhedral structures. Lead is easily extracted from its ; prehistoric people in knew of it. , a principal of lead, often bears , interest in which helped initiate widespread extraction and use of lead in . Lead production declined after the fall of Rome and did not reach comparable levels until the . In 2014, annual global production of lead was about ten million tonnes, over half of which was from recycling. Lead's high , low melting point, , and relative inertness to oxidation make it useful. These properties, com- bined with its relative abundance and low cost, resulted in its extensive use in construction, , batteries, and , , , , fusible alloys, white , leaded , and radiation shielding. In the late 19th century, lead's was recognized, and its use has since been phased out of many applications. Lead is a toxin that accumulates in soft tissues and , it acts as a damaging the and interferences with the function of biological . It is particularly problematic in children: even if blood levels are promptly normalized with treatment, neurological disorders, such as brain damage and behavioral prob- lems, may result

Physical properties radii from (atomic number 57) to (71), and the relatively small radii of the elements after (72). This is due to poor shielding of the nucleus Atomic by the 4f . The combined first four A lead has 82 electrons, arranged in an energies of lead exceed those of configuration of [Xe]4f145d106s26p2. The combined first ,[1]contrary to what would predict. and second ionization energies—the total energy re- Relativistic effects, which become significant in heavier quired to remove the two 6p electrons—is close to that , contribute to this behavior.[a] One such effect is of tin, lead's upper neighbor in the . This is the inert pair effect: the 6s electrons of lead become re- unusual; ionization energies generally fall going down a luctant to participate in bonding, which to ele- group, as an element's outer electrons become more vated ionization energies and makes the distance be- distant from the nucleus, and more shielded by smaller tween nearest atoms in crystalline lead unusually orbitals. The similarity of ionization energies is caused long.[3] by the —the decrease in element Lead's lighter carbon group congeners form stable or metastable allotropes with the tetrahedrally coordi- nated and covalently bonded cubic structure. 1 Department of Optimal Control, Faculty of Computational Mathe- matics and Cybernetics, Moscow State University, Moscow, The energy levels of their outer s- and p-orbitals are 3 *Author correspondence: [email protected] close enough to allow mixing into four hybrid sp orbit- ORCID: [0000-0000-0000-0001] als. In lead, the inert pair effect increases the separation Licensed under: CC-BY-SA between its s- and p-orbitals, and the gap cannot be Received 22-11-2017; accepted 03-07-2018

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overcome by the energy that would be released by ex- The melting point of lead—at 327.5 °C (621.5 °F)[24]—is tra bonds following hybridization.[4] Rather than having very low compared to most .[15][g] Its a structure, lead forms metallic bonds in of 1749 °C (3180 °F)[24] is the lowest among the carbon which only the p-electrons are delocalized and shared group elements. The electrical resistivity of lead at 20 between the Pb2+ . Lead consequently has a face- °C is 192 nanoohm-meters, almost an order of magni- centered cubic structure[5] like the similarly sized[6] diva- tude higher than those of other industrial metals (cop- lent metals and .[7][b][c][d] per at 15.43 nΩ·m; 20.51 nΩ·m; and at 24.15 nΩ·m).[26] Lead is a superconductor at tempera- Bulk tures lower than 7.19 ;[27] this is the highest critical temperature of all type-I superconductors and the third Pure lead has a bright, silvery appearance with a hint of highest of the elemental superconductors.[28] blue.[12] It tarnishes on contact with moist air, and takes on a dull appearance the hue of which depends on the prevailing conditions. Characteristic properties of lead include high density, malleability, ductility,[e] and high Natural lead consists of four stable isotopes with mass resistance to due to .[13] numbers of 204, 206, 207, and 208,[29] and traces of five short-lived radioisotopes.[30] The main , Lead's close-packed face-centered cubic structure and with information on percent abundance, half-life, and high atomic result in a density[15] of 11.34 g/cm3, decay mode and product, are listed in Table 1. The high which is greater than that of common metals such as number of isotopes is consistent with lead's atomic (7.87 g/cm3), (8.93 g/cm3), and (7.14 number being even.[h] Lead has a of pro- g/cm3).[16] This density is the origin of the idiom to go tons (82), for which the nuclear model accurately over like a lead balloon.[17][18][f] Some rarer metals are predicts an especially stable nucleus.[31] Lead-208 has denser: and gold are both at 19.3 g/cm3, and 126 , another magic number, which may ex- —the densest metal known—has a density of plain why lead-208 is extraordinarily stable.[31] 22.59 g/cm3, almost twice that of lead.[19] With its high atomic number, lead is the heaviest ele- Lead is a very soft metal with a Mohs hardness of 1.5; it ment whose natural isotopes are regarded as stable; can be scratched with a fingernail.[20] It is very malleable lead-208 is the heaviest stable nucleus. This title was and quite ductile.[21] The of lead—a meas- formerly held by , with an atomic number of 83, ure of its ease of compressibility—is 45.8 GPa. In com- until its only primordial , bismuth-209, was parison, that of aluminium is 75.2 GPa; copper 137.8 found in 2003 to decay very slowly.[i] The four stable iso- GPa; and mild 160–169 GPa.[22] Lead's tensile topes of lead could theoretically undergo strength, at 12–17 MPa, is low (that of aluminium is 6 to isotopes of mercurywith a release of energy, but this times higher, copper 10 times, and mild steel 15 times has not been observed for any of them; their predicted higher); it can be strengthened by adding small half-lives range from 1035 to 10189 years.[34] amounts of copper or .[23] Three of the stable isotopes are found in three of the four major decay chains: lead-206, lead-207, and lead- 208 are the final decay products of -238, ura- nium-235, and -232, respectively. These decay

Isotope Decay

abundance half-life (t1/2) mode product 202 4 202 Pb syn 5.25(28)×10 y ε Tl 204 Pb 1.4% stable 205 7 205 Pb trace 1.53(7)×10 y ε Tl 206Pb 24.1% stable 207Pb 22.1% stable 208Pb 52.4% stable 209 − 209 Pb trace 3.253(14) h β Bi 210 − 210 Pb trace 22.3(22) y β Bi 211 − 211 Pb trace 36.1(2) min β Bi 212 − 212 Pb trace 10.64(1) h β Bi 214 − 214 Pb trace 26.8(9) min β Bi

Figure 1 | A sample of lead solidified from the molten state. Table 1 | Main isotopes of lead. Isotopic abundances vary Juergen Kummer, CC-BY 3.0 greatly by sample. : 207.2(1)[14] (Ar, standard)

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samples by measuring its ratio to lead-206 (both iso- topes are present in a single ).[42] In total, 43 lead isotopes have been synthesized, with mass numbers 178–220.[29] Lead-205 is the most stable radioisotope, with a half-life of around 1.5×107 years.[j] The second-most stable is lead-202, which has a half- life of about 53,000 years, longer than any of the natural trace radioisotopes.[29]

Chemistry

Bulk lead exposed to moist air forms a protective layer Figure 2 | The Holsinger , the largest piece of the of varying composition. Lead(II) carbonate is a common [44][45][46] Canyon Diablo meteorite. Uranium–lead dating and lead– constituent; the sulfate or chloride may also be lead dating on this meteorite allowed refinement of the age present in urban or maritime settings.[47] This layer of the to 4.55 billion ± 70 million years. makes bulk lead effectively in the air.[47] Marcin Wichary, CC-BY 2.0 Finely powdered lead, as with many metals, is pyro- phoric,[48] and burns with a bluish-white flame.[49] chains are called the uranium chain, the chain, and the thorium chain.[35] Their isotopic concentrations reacts with lead at room temperature, forming in a natural sample depends greatly on the pres- lead(II) fluoride. The reaction with is similar but ence of these three parent uranium and thorium iso- requires heating, as the resulting chloride layer dimin- topes. For example, the relative abundance of lead-208 ishes the reactivity of the elements.[47] Molten lead re- can range from 52% in normal samples to 90% in tho- acts with the chalcogensto give lead(II) chalcogeni- rium ores;[36] for this reason, the standard atomic des.[50] weight of lead is given to only one decimal place.[37] As Lead metal resists sulfuric and phosphoric but not time passes, the ratios of lead-206 and lead-207 to lead- hydrochloric or ; the outcome depends on sol- 204 increase, since the former two are supplemented ubility and subsequent passivation of the product by of heavier elements while the lat- .[51] Organic acids, such as , dissolve lead ter is not; analysis of lead-207/lead-204 ratios versus in the presence of .[47] lead-206/lead-204 ratios constitutes lead–lead dating. Concentrated alkalis will dis- As uranium decays into lead, their relative amounts solve lead and form plum- change; analysis of uranium-238/lead-206 ratios versus bites.[52] uranium-235/lead-207 ratios constitutes uranium–lead dating.[38] Lead-207 exhibits nuclear magnetic reso- nance, a property that has been used to study its com- Inorganic compounds pounds in solution and state,[39][40] including in hu- Lead shows two main oxidation man body.[41] states: +4 and +2. The tetrava- Apart from the stable isotopes, which make up almost lent state is common for the car- all lead that exists naturally, there are trace quantities bon group. The divalent state is of a few radioactive isotopes. One of them is lead-210; rare for carbon and , minor although it has a half-life of only 22.3 years,[29] small for , important (but quantities occur in nature because lead-210 is produced not prevailing) for tin, and is the more important of the two oxi- by a long decay series that starts with uranium-238 [47] (which has been present for billions of years on Earth). dation states for lead. This is Lead-211, -212, and -214 are present in the decay chains attributable to relativistic ef- of uranium-235, thorium-232, and uranium-238, respec- fects, specifically the inert pair tively, so traces of all three of these lead isotopes are effect, which manifests itself when there is a large difference found naturally. Minute traces of lead-209 arise from in between the very rare of -223, one of the Figure 3 | daughter products of natural uranium-235. Lead-210 is lead and , , or : lead colors particularly useful for helping to identify the ages of anions, leading to a significant flame pale blue partial positive charge on lead. Herge, public domain

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Figure 4 | Polymorphs of lead(II) oxide, (α-PbO, left) and (β-PbO, right). Hubertus Giefers, public domain

The result is a stronger contraction of the lead 6s orbital than is the case for the 6p orbital, making it rather inert in ionic compounds. The inert pair effect is less applica- Figure 5 | Lead and oxygen in a tetragonal unit cell of ble to compounds in which lead forms covalent bonds lead(II,IV) oxide. with elements of similar electronegativity, such as car- Lead bon in organolead compounds. In these, the 6s and 6p Oxygen orbitals remain similarly sized and sp3 hybridization is Ben Mills, public domain still energetically favorable. Lead, like carbon, is pre- dominantly tetravalent in such compounds.[53] Lead commonly reacts with heavier . Lead is a , a photoconductor, and an There is a relatively large difference in the electronega- extremely sensitive radiation detector. The tivity of lead(II) at 1.87 and lead(IV) at 2.33. This differ- other two chalcogenides, lead and lead tellu- ence marks the reversal in the trend of increasing sta- ride, are likewise photoconducting. They are unusual in bility of the +4 oxidation state going down carbon that their color becomes lighter going down the group; tin, by comparison, has values of 1.80 in the +2 group.[61] oxidation state and 1.96 in the +4 state.[54] Lead dihalides are -characterized; this includes the [62] Lead(II) diastatide, and mixed , such as PbFCl. The rel- ative insolubility of the latter forms a useful basis for the Lead(II) compounds are characteristic of the inorganic gravimetricdetermination of fluorine. The difluoride chemistry of lead. Even strong oxidizing agents like flu- was the first solid ionically conducting compound to be orine and chlorine react with lead to give only PbF2 and discovered (in 1834, by ).[63] The other [47] PbCl2. Lead(II) ions are usually colorless in solu- dihalides decompose on exposure to ultraviolet or visi- [55] tion. No simple is found; in aqueous solu- ble light, especially the diiodide.[64] Many lead(II) pseu- tion, the lead(II) undergoes a series of pH-depend- dohalides are known, such as the cyanide, cyanate, and ent hydrolysis and condensation reactions, including thiocyanate.[61][65] Lead(II) forms an extensive variety of Pb(OH)+ and the most common hydrolysis product, 2− halide coordination complexes, such as [PbCl4] , 4+ 4 4 4− 5n− [64] [Pb4(OH)4]4+.b (OH) ] (in which the hydroxyl ions act [PbCl6] , and the [Pb2Cl9]n chain anion. as bridging ).[56][57] Lead(II) ions are not reducing agents as tin(II) ions are. Techniques for identifying the Lead(II) sulfate is insoluble in , like the sulfates of presence of the Pb2+ ion in water generally rely on the other heavy divalent cations. Lead(II) nitrate and precipitation of lead(II) chloride using dilute hydrochlo- lead(II) acetate are very soluble, and this is exploited in [66] ric acid. As the chloride salt is sparingly soluble in water, the synthesis of other . in very dilute solutions the precipitation of lead(II) sul- fide is achieved by bubbling sulfide through Lead(IV) [58] the solution.. Few inorganic lead(IV) compounds are known. They are Lead monoxide exists in two polymorphs, litharge α- only formed in highly oxidizing solutions and do not [67] PbO (red) and massicot β-PbO (yellow), the latter being normally exist under standard conditions. Lead(II) stable only above around 488 °C. It is the most com- oxide gives a mixed oxide on further oxidation, Pb3O4. It monly used of lead.[59] There is no is described as lead(II,IV) oxide, or structurally lead(II) hydroxide; increasing the pH of solutions of 2PbO·PbO2, and is the best-known mixed lead lead(II) salts leads to hydrolysis and condensation.[60]

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compound. Organolead is a strong , capable of oxidiz- Lead can form multiply-bonded chains, a property it ing to shares with its lighter homologs in the carbon group. chlorine gas.[68] This is The capacity for decreases going down the because the expected group due to decreasing . The Pb–Pb bond energy is over three and a half times lower than that of PbCl4 that would be pro- [50] duced is unstable and the C–C bond. With itself lead can build metal–metal [82] spontaneously decom- bonds of an order up to three. With carbon, lead [69] forms organolead compounds similar to, but generally poses to PbCl2 and Cl2. [83] Figure 6 | The capped square Analogously to lead less stable than, typical organic compounds (due to 4− [73] [56] antiprismatic anion [Pb9] . monoxide, lead dioxide is the Pb–C bond being rather weak). This makes the Ben Mills, public domain capable of forming plum- of lead far less wide-ranging [84] bate anions. Lead disul- than that of tin. Lead predominantly forms organ- fide[70] and lead diselenide[71] are only stable at high olead(IV) compounds, even when starting with inor- pressures. , a yellow crystalline pow- ganic lead(II) reactants; very few organolead(II) com- der, is stable, but less so than the difluoride. Lead tetra- pounds are known. The most well-characterized excep- 5 [84] chloride (a yellow oil) decomposes at room tempera- tions are Pb[CH(SiMe3)2]2 and Pb(η -C5H5)2. ture, lead tetrabromide is less stable still, and the exist- The lead analog of the simplest , me- ence of lead tetraiodide is questionable.[72] thane, is . Plumbane may be obtained in a re- action between metallic lead and atomic hydrogen.[85] Other oxidation states It is thermodynamically unstable and its chemistry has [86] Some lead compounds exist in formal oxidation states not been determined. Two simple derivatives, tetra- other than +4 or +2. Lead(III) may be obtained, as an in- methyllead and , are the best-known or- termediate between lead(II) and lead(IV), in larger or- ganolead compounds. These compounds are relatively ganolead complexes; this oxidation state is not stable, stable: tetraethyllead only starts to decompose if [87] [88] as both the lead(III) ion and the larger complexes con- heated or if exposed to sunlight or ultraviolet light. taining it are radicals.[74][75][76] The same applies for (Tetraphenyllead is even more thermally stable, de- [84] lead(I), which can be found in such species.[77] composing at 270 °C. ) With metal, lead read- ily forms an equimolar that reacts with hal- Numerous mixed lead(II,IV) oxides are known. When PbO2 is heated in air, it becomes Pb12O19 at 293 °C, Pb12O17 at 351 °C, Pb3O4 at 374 °C, and finally PbO at 605 °C. A further , Pb2O3, can be obtained at high pressure, along with several non-stoichiometric phases. Many of them show defective struc- tures in which some oxygen atoms are replaced by va- cancies: PbO can be considered as having such a struc- ture, with every alternate layer of oxygen atoms ab- sent.[78] Negative oxidation states can occur as Zintl phases, as either free lead anions, as in Ba2Pb, with lead formally being lead(−IV),[79] or in oxygen-sensitive ring-shaped or polyhedral cluster ions such as the trigonal bipyram- 2− idal Pb5 ion, where two lead atoms are lead(−I) and three are lead(0).[80] In such anions, each atom is at a polyhedral vertex and contributes two electrons to each along an edge from their sp3 hybrid or- [56] bitals, the other two being an external . They Figure 7 | Structure of a tetraethyllead may be made in liquid via the reduction of Lead lead by sodium.[81] Carbon Hydrogen Jynto, public domain

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ides to form organometalliccompounds such as tetrae- thyllead.[89] The oxidizing nature of many organolead compounds is usefully exploited: lead tetraacetate is an important laboratory reagent for oxidation in organic synthesis,[90] and tetraethyllead was once produced in larger quantities than any other organometallic com- .[84] Other organolead compounds are less chem- ically stable.[83] For many organic compounds, a lead an- alog does not exist.[85]

Origin and occurrence

In space

Lead's per-particle abundance in the is Figure 8 | Chart of the final part of the s-process, 0.121 ppb (parts per billion).[91][k] This figure is two and from to . Red lines and circles repre- a half times higher than that of , eight times sent captures; blue arrows represent beta decays; more than mercury, and seventeen times more than the arrow represents an alpha decay; cyan arrows rep- resent electron captures. gold.[91] The amount of lead in the is slowly in- creasing[92] as most heavier atoms (all of which are un- occurring in stars. The two main modes of capture are [93] stable) gradually decay to lead. The abundance of the s- and r-processes.[95] lead in the Solar System since its formation 4.5 billion years ago has increased by about 0.75%.[94] The solar In the s-process (s is for "slow"), captures are separated system abundances table shows that lead, despite its by years or decades, allowing less stable nuclei to un- [96] relatively high atomic number, is more prevalent than dergo . A stable -203 nucleus can most other elements with atomic numbers greater than capture a neutron and become thallium-204; this un- 40.[91] dergoes beta decay to give stable lead-204; on captur- ing another neutron, it becomes lead-205, which has a Primordial lead—which comprises the isotopes lead- half-life of around 15 million years. Further captures re- 204, lead-206, lead-207, and lead-208—was mostly cre- sult in lead-206, lead-207, and lead-208. On capturing ated as a result of repetitive processes

Atomic Relative number Element amount

42 0.798

46 0.440

50 Tin 1.146

78 Platinum 0.417

80 Mercury 0.127 82 Lead 1.000

90 Thorium 0.011

92 Uranium 0.003

Table 2 | Solar System abundances[91] Figure 9 | Lead is a fairly common element in the Earth's crust for its high atomic number (82). Most elements of atomic number greater than 40 are less abundant. Gordon Haxel, Sara Boore, Susan Mayfield, public domain

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another neutron, lead-208 becomes lead-209, which quickly decays into bismuth-209. On capturing another neutron, bismuth-209 becomes bismuth-210, and this The modern English word "lead" is of Germanic origin; beta decays to polonium-210, which alpha decays to it comes from the leed and lead-206. The cycle hence ends at lead-206, lead-207, lēad (with the macron above the "e" signifying that the lead-208, and bismuth-209.[97] vowel sound of that letter is long).[111] The Old English word is derived from the hypothetical reconstructed In the r-process (r is for "rapid"), captures happen faster Proto-Germanic *lauda- ("lead").[112] According to lin- than nuclei can decay.[98] This occurs in environments guistic theory, this word bore descendants in multiple with a high neutron density, such as a or the Germanic languages of exactly the same meaning.[112] merger of two neutron stars. The neutron involved may be on the order of 1022 neutrons per square centi- The origin of the Proto-Germanic *lauda- is not agreed meter per second.[99] The r-process does not form as in the linguistic community. One hypothesis suggests it much lead as the s-process.[100] It tends to stop once is derived from Proto-Indo-European *lAudh- ("lead"; neutron-rich nuclei reach 126 neutrons.[101] At this capitalization of the vowel is equivalent to the mac- point, the neutrons are arranged in complete shells in ron).[113] Another hypothesis suggests it is borrowed the , and it becomes harder to energeti- from Proto-Celtic *φloud-io- ("lead"). This word is re- cally accommodate more of them.[102] When the neu- lated to the Latin plumbum, which gave the element its tron flux subsides, these nuclei beta decay into stable Pb. The word *φloud-io- is thought to , , and platinum.[103] be the origin of Proto-Germanic *bliwa- (which also means "lead"), from which stemmed the German On Earth Blei.[114] Lead is classified as a chalcophile under the Gold- The name of the chemical element is not related to the schmidt classification, meaning it is generally found verb of the same spelling, which is derived from Proto- combined with .[104] It rarely occurs in its native, Germanic *laidijan- ("to lead").[115] metallic form.[105] Many lead are relatively light and, over the course of the Earth's history, have re- mained in the crust instead of sinking deeper into the History Earth's interior. This accounts for lead's relatively high crustal abundance of 14 ppm; it is the 38th most abun- Prehistory and early history dantelement in the crust.[106][l] Metallic lead beads dating back to 7000–6500 BCE have The main lead- is galena (PbS), which is been found in Asia Minor and may represent the first ex- mostly found with zinc ores.[108] Most other lead miner- ample of metal .[117] At that time lead had few als are related to galena in some way; boulangerite, (if any) applications due to its softness and dull appear- Pb5Sb4S11, is a mixed sulfide derived from galena; an- ance.[117] The major reason for the spread of lead pro- glesite, PbSO4, is a product of galena oxidation; and ce- duction was its association with silver, which may be russite or ore, PbCO3, is a decomposition obtained by burning galena (a common lead min- product of galena. , tin, antimony, silver, gold, eral).[118] The Ancient Egyptians were the first to use copper, and bismuth are common impurities in lead lead minerals in , an application that spread minerals.[108] to Ancient and beyond;[119] the Egyptians may World lead resources exceed 2 billion tons. Significant have used lead for sinkers in fishing nets, glazes, [118] deposits are located in , , Ireland, Mex- , enamels, and for ornaments. Various civili- ico, , Portugal, Russia, and the United States. zations of the used lead as a writing [118] Global reserves—resources that are economically feasi- material, as currency, and for construction. Lead ble to extract—totaled 88 million tons in 2016, of which was used in the Ancient Chinese royal court as a stimu- [118] [120] [121] Australia had 35 million, China 17 million, and Russia 6.4 lant, as currency, and as a contraceptive; the [118] million.[109] Indus Valley civilization and the Mesoamericans used it for making amulets; and the eastern and south- Typical background concentrations of lead do not ex- ern African peoples used lead in drawing.[122] ceed 0.1 μg/m3 in the atmosphere; 100 mg/kg in ; and 5 μg/L in freshwater and .[110] Classical era Because silver was extensively used as a decorative ma- terial and an exchange medium, lead deposits came to

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conferred an agreeable due to the formation of " of lead" (lead(II) acetate), whereas copper or vessels could impart a bitter flavor through for- mation.[132] The Roman author re- ported the health dangers of lead[133] and modern writers have suggested that lead played a major role in the decline of the .[134][135][m] Other researchers have criticized such claims, pointing out, for in- Figure 10 | World lead production peaking in the Roman and the Industrial Rev- stance, that not all abdominal pain olution.[116] is caused by .[137][138] Fox 52, CC-BY-SA 4.0 According to archaeological re- be worked in Asia Minor since 3000 BCE; later, lead de- search, Roman lead pipes in- posits were developed throughout Mediterra- creased lead levels in but such an effect was nea.[124][125] "unlikely to have been truly harmful".[139][140] When lead poisoning did occur, victims were called "saturnine", Rome's territorial expansion in and across the dark and cynical, after the ghoulish father of the gods, Mediterranean, and its development of , led to it . By association, lead was considered the father becoming the greatest producer of lead during the clas- of all metals.[141] Its status in Roman society was low as sical era, with an estimated annual output peaking at it was readily available[142] and cheap.[143] 80,000 tonnes. Like their predecessors, the Romans ob- tained lead mostly as a by-product of silver smelt- Confusion with tin and antimony ing.[116][126] During the classical era (and even up to the 17th cen- “This metal was by far the most used material in classical antiq- tury), tin was often not distinguished from lead: Ro- uity, and it is appropriate to refer to the (Roman) Lead Age. Lead mans called lead plumbum nigrum ("black lead"), and tin was to the Romans what plastic is to us.” plumbum candidum ("bright lead"). The association of Heinz Eschnauer and Markus Stoeppler lead and tin can be seen in other languages: the word "Wine—An enological specimen bank", 1992[127] olovo in Czech translates to "lead", but in Russian the cognate олово (olovo) means "tin".[144] To add to the Lead was used for making water pipes; the Latin word confusion, lead bore a close relation to antimony: both for the metal, plumbum, is the origin of the English word elements commonly occur as (galena and stib- "plumbing". Its ease of working and resistance to corro- sion[128] ensured its widespread use in other applications including pharmaceuticals, roofing, currency, and war- fare.[129][130][131] Writers of the time recommended lead (or lead-coated) vessels for the preparation of sweeten- ers and preservatives added to wine and food. The lead

Figure 11 | Ancient Greek lead bullets with a winged Figure 12 | Roman lead pipes[n] thunderbolt molded on one side and the inscription "ΔΕΞΑΙ" Wolfgang Sauber, CC-BY-SA 3.0 ("take that" or "catch") on the other side[123] Marie-Lan Nguyen, public domain

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nite), often together. Pliny incorrectly wrote that stib- Christian rites by a papal bull in 1498, but it continued nite would give lead on heating, instead of anti- to be imbibed and resulted in mass up to the mony.[145] In countries such as Turkey and , the late 18th century.[148][153] Lead was a key material in originally Persian name surma came to refer to either parts of the , which was invented around antimony sulfide or lead sulfide,[146] and in some lan- 1440; lead dust was commonly inhaled by print work- guages, such as Russian, gave its name to antimony ers, causing lead poisoning.[154] Firearms were invented (сурьма).[147] at around the same time, and lead, despite being more expensive than iron, became the chief material for mak- Middle Ages and the Renaissance ing bullets. It was less damaging to iron gun barrels, had a higher density (which allowed for better retention of Lead mining in Western Europe declined after the fall of velocity), and its lower melting point made the produc- the , with Arabian Iberia being tion of bullets easier as they could be made using a [148][149] the only region having a significant output. The wood .[155] Lead, in the form of Venetian ceruse, was largest production of lead occurred in South and East extensively used in cosmetics by Western European ar- Asia, especially China and India, where lead mining istocracy as whitened faces were regarded as a sign of [149] grew strongly. modesty.[156][157] This practice later expanded to white In Europe, lead production only began to revive in the wigs and eyeliners, and only faded out with the French 11th and 12th centuries, when it was again used for Revolution in the late 18th century. A similar fashion ap- roofing and piping. Starting in the 13th century, lead peared in in the 18th century with the emergence was used to create stained .[151] In the European of the geishas, a practice that continued long into the and Arabiantraditions of , lead was considered 20th century. The white faces of women "came to rep- an impure metal which, by the separation, purifi- resent their feminine virtue as Japanese women",[158] cation and balancing of its constituent essences, could with lead commonly used in the whitener.[159] be transformed to pure and incorruptible gold.[152] Dur- ing the period, lead was used increasingly for adulterat- Outside Europe and Asia ing wine. The use of such wine was forbidden for use in In the , lead was produced soon after the ar- rival of European settlers. The earliest recorded lead production dates to 1621 in the English Colony of Vir- ginia, fourteen years after its foundation.[160] In Aus- tralia, the first mine opened by colonists on the conti- nent was a lead mine, in 1841.[161] In Africa, lead mining and smelting were known in the Benue Trough[162] and the lower Congo Basin, where lead was used for trade with Europeans and as a currency by the 17th cen- tury,[163] well before the .

Industrial Revolution In the second half of the 18th century, Britain, and later continental Europe and the United States, experienced

Figure 13 | of was commonly depicted Figure 14 | Lead mining in the upper Mississippi with a whitened face. Lead in face whiteners is thought to River region in the United States in 1865. have contributed to her death.[150] John Barber and Henry Howe, public domain Nicholas Hilliard, public domain

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the Industrial Revolution. This was the first time during major lead production in the late 20th century.[175] Un- which production rates exceeded those of Rome.[116] like the European communist countries, China was Britain was the leading producer, losing this status by largely unindustrialized by the mid-20th century; in the mid-19th century with the depletion of its mines 2004, China surpassed Australia as the largest producer and the development of lead mining in , Spain, of lead.[176] As was the case during European industrial- and the United States.[164] By 1900, the United States ization, lead has had a negative effect on health in was the leader in global lead production, and other non- China.[177] European nations—, , and Australia— had begun significant production; production outside Europe exceeded that within.[165] A great share of the Production demand for lead came from plumbing and painting— lead paints were in regular use.[166] At this time, more Production of lead is increasing worldwide due to its use [178] (working class) people were exposed to the metal and in lead–acid batteries. There are two major catego- lead poisoning cases escalated. This led to research into ries of production: primary from mined ores, and sec- the effects of lead intake. Lead was proven to be more ondary from scrap. In 2014, 4.58 million metric tons dangerous in its fume form than as a solid metal. Lead came from primary production and 5.64 million from poisoning and were linked. The effects of chronic secondary production. The top three producers of ingestion of lead, including mental disorders, were also mined lead concentrate in that year were China, Aus- studied in the 19th century. The first laws aimed at de- tralia, and the United States. The top three producers creasing lead poisoning in factories were enacted dur- of refined lead were China, the United States, and [179] ing the 1870s and 1880s in the United Kingdom.[166] South Korea. According to the International Re- source Panel's Metal Stocks in Society report of 2010, Modern era the total amount of lead in use, stockpiled, discarded, or dissipated into the environment, on a global basis, is Further evidence of the threat that lead posed to hu- 8 kg per capita. Much of this is in more developed coun- mans was discovered in the late 19th and early 20th tries (20–150 kg per capita) rather than less developed centuries. Mechanisms of harm were better under- ones (1–4 kg per capita).[180] stood, lead blindness was documented, and the ele- The primary and secondary lead production processes ment was phased out of public use in the United States are similar. Some primary production plants now sup- and Europe. The United Kingdom introduced manda- plement their operations with scrap lead, and this trend tory factory inspections in 1878 and appointed the first is likely to increase in the future. Given adequate tech- Medical Inspector of Factories in 1898; as a result, a 25- niques, lead obtained via secondary processes is indis- fold decrease in lead poisoning incidents from 1900 to tinguishable from lead obtained via primary processes. 1944 was reported.[167] The last major human exposure Scrap lead from the building trade is usually fairly clean to lead was the addition of tetraethyllead to gasoline as and is re-melted without the need for smelting, though an , a practice that originated in the is sometimes needed. Secondary lead produc- United States in 1921. It was phased out in the United tion is therefore cheaper, in terms of energy require- States and the by 2000.[166] Most Euro- ments, than is primary production, often by 50% or pean countries banned lead —commonly used be- more.[181] cause of its opacity and water resistance[168]—for interi- ors by 1930.[169] Primary In the 1970s, the United States and Western European countries introduced legislation to reduce lead air pol- Most lead ores contain a low percentage of lead (rich lution.[170][171] The impact was significant: the share of ores have a typical content of 3–8%) which must be con- [182] people in the United States with elevated blood lead centrated for extraction. During initial processing, levels fell from 77.8% in 1976–1980 to 2.2% in 1991– ores typically undergo crushing, dense-medium separa- 1994.[172] The main product made of lead by the end of tion, grinding, , and drying. The resulting the 20th century was the lead–acid battery,[173] which concentrate, which has a lead content of 30–80% by [182] posed no direct threat to humans. From 1960 to 1990, mass (regularly 50–60%), is then turned into (im- lead output in the Western Bloc grew by a third.[174] The pure) lead metal. share of the world's lead production by the There are two main ways of doing this: a two-stage pro- increased from 10% to 30%, from 1950 to 1990, with cess involving followed by extrac- the being the world's largest producer tion, carried out in separate vessels; or a direct process during the mid-1970s and the 1980s, and China starting in which the extraction of the concentrate occurs in a

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single vessel. The latter has become the most common Very pure lead can be obtained by processing smelted route, though the former is still significant.[183] lead electrolytically using the Betts process. of impure lead and of pure lead are placed in an Two-stage process of lead fluorosilicate (PbSiF6). Once electri- cal potential is applied, impure lead at the dis- First, the sulfide concentrate is roasted in air to oxidize solves and plates onto the , leaving the majority the lead sulfide:[184] of the impurities in solution.[188][190] This is a high-cost

2 PbS(s) + 3 O2(g) → 2 PbO(s) + 2 SO2(g) process and thus mostly reserved for refining bullion containing high percentages of impurities.[191] As the original concentrate was not pure lead sulfide, roasting yields not only the desired lead(II) oxide, but a Direct process mixture of oxides, sulfates and silicates of lead and other metals contained in the ore.[185] This impure lead In this process, lead bullion and is obtained directly oxide is reduced in a -fired blast furnace to the from lead concentrates. The lead sulfide concentrate is (again, impure) metal:[186] melted in a furnace and oxidized, forming lead monox- ide. Carbon (as coke or gas[o]) is added to the mol- 2 PbO(s) + C(s) → 2 Pb(s) + CO2(g) ten charge along with fluxing agents. The lead monox- ide is thereby reduced to metallic lead, in the midst of a Impurities are mostly arsenic, antimony, bismuth, zinc, slag rich in lead monoxide.[183] copper, silver, and gold. The melt is treated in a rever- beratory furnace with air, steam, and sulfur, which oxi- As much as 80% of the lead in very high-content initial dizes the impurities except for silver, gold, and bismuth. concentrates can be obtained as bullion; the remaining Oxidized contaminants float to the top of the melt and 20% forms a slag rich in lead monoxide. For a low-grade are skimmed off.[187][188] Metallic silver and gold are re- feed, all of the lead can be oxidized to a high-lead moved and recovered economically by means of the slag.[183]Metallic lead is further obtained from the high- , in which zinc is added to lead. The zinc, lead (25–40%) via submerged fuel combustion or which is immiscible in lead, dissolves in silver and gold. injection, reduction assisted by an electric furnace, or a The zinc solution can be separated from the lead, and combination of both.[183] the silver and gold retrieved.[189][188] De-silvered lead is freed of bismuth by the Betterton–Kroll process, treat- Output ing it with metallic calcium and . The result- (thousand [188] ing bismuth can be skimmed off. Country tons) China 2,400 Australia 500 United States 335 Peru 310 Mexico 250 Russia 225 India 135 80 76 Turkey 75 Iran 41 Kazakhstan 41 40 40 North Korea 35 Ireland 33 Macedonia 33 Other countries 170

Table 3 | World's largest mining Figure 15 | Primary production of lead since 1840 countries of lead, 2016[109] Borvan53, CC-BY-SA 4.0

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Alternatives be cast with minimal technical equipment; and it is denser than other common metals, which allows for Research on a cleaner, less energy-intensive lead ex- better retention of velocity. Concerns have been raised traction process continues; a major drawback is that ei- that lead bullets used for can damage the envi- ther too much lead is lost as waste, or the alternatives ronment.[p] result in a high sulfur content in the resulting lead metal. Hydrometallurgical extraction, in which anodes Lead's high density and resistance to corrosion have of impure lead are immersed into an electrolyte and been exploited in a number of related applications. It is pure lead is deposited onto a cathode, is a technique used as ballast in sailboat keels;[200] its density allows it that may have potential.[192] to take up a small volume and minimize water re- sistance, thus counterbalancing the heeling effect of Secondary wind on the sails. It is used in weight belts to counteract the diver's buoyancy.[201] In 1993, the base Smelting, which is an essential part of the primary pro- of the Leaning Tower of Pisa was stabilized with 600 duction, is often skipped during secondary production. tonnes of lead.[202] Because of its corrosion resistance, It is only performed when metallic lead had undergone lead is used as a protective sheath for underwater ca- [181] significant oxidation. The process is similar to that of bles.[203] primary production in either a blast furnace or a rotary furnace; blast furnaces produce hard lead (10% anti- Lead has many uses in the construction industry; lead mony) while reverberatory and rotary kiln furnaces pro- sheets are used as in roofing mate- duced semisoft lead (3–4% antimony).[193] The Isasmelt rial, cladding, flashing, gutters and gutter joints, and on process is a more recent method that may act as an ex- parapets.[204][205] Detailed lead moldings are used tension to primary production; battery paste from as decorative motifs to fix lead sheet. Lead is still used spent lead–acid batteries has sulfur removed by treat- in statues and sculptures,[q] including for armatures.[207] ing it with alkali, and is then treated in a coal-fueled fur- In the past it was often used to balance the wheels of nace in the presence of oxygen, which yields impure cars; for environmental reasons this use is being phased lead, with antimony the most common impurity.[194] out in favor of other materials.[109] Refining of secondary lead is similar to that of primary Lead is added to copper alloys such as and bronze, lead. Some refining processes may be skipped depend- to improve machinability and for its lubricating quali- ing on the material recycled and its potential contami- ties. Being practically insoluble in copper, lead forms [195] nation. solid globules in imperfections throughout the alloy, Of the sources of lead for recycling, lead–acid batteries such as grain boundaries. In low concentrations, as well are the most important; lead , sheet, and cable as acting as a , the globules hinder the for- sheathing are also significant.[181] mation of swarf as the alloy is worked, thereby improv- ing machinability. Copper alloys with larger concentra- tions of lead are used in bearings. The lead provides lu- Applications brication, and the copper provides the load-bearing support.[208] Contrary to popular belief, leads in wooden pen- cils have never been made from lead. When the pencil originated as a wrapped writing tool, the par- ticular type of graphite used was named plumbago (lit- erally, act for lead or lead mockup).[197]

Elemental form Lead metal has several useful mechanical properties, including high density, low melting point, ductility, and relative inertness. Many metals are superior to lead in some of these aspects but are generally less common and more difficult to extract from parent ores. Lead's toxicity has led to its phasing out for some uses.[198]

Lead has been used for bullets since their invention in Figure 16 | Bricks of lead (alloyed with 4% antimony) are used the Middle Ages. It is inexpensive; its low melting point as radiation shielding.[196] means small arms ammunition and shotgun pellets can Loren Chang, public domain

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Figure 17 | A 17th-century gold-coated lead sculpture Figure 18 | Coyau, CC-BY-SA 3.0 Paolo Neo, public domain

Lead's high density, atomic number, and formability Compounds form the basis for use of lead as a barrier that absorbs Lead compounds are used as, or in, coloring agents, ox- sound, vibration, and radiation.[209] Lead has no natural idants, plastic, , glass, and . resonance frequencies;[209] as a result, sheet-lead is While lead paints are phased out in Europe and North used as a sound deadening layer in the walls, floors, and America, they remain in use in less developed countries ceilings of sound studios.[210] Organ pipes are often such as China[223] or India.[224] Lead-based coloring made from a lead alloy, mixed with various amounts of agents are used in glazes and glass, especially tin to control the tone of each pipe.[211][212] Lead is an es- for red and yellow shades.[225] Lead tetraacetate and tablished shielding material from radiation in nuclear lead dioxide are used as oxidizing agents in organic science and in X-ray rooms[213] due to its denseness and chemistry. Lead is frequently used in the polyvinyl chlo- high attenuation coefficient.[214] Molten lead has been ride coating of electrical cords.[226][227] It can be used to used as a for lead-cooled fast reactors.[215] treat wicks to ensure a longer, more even burn. The largest use of lead in the early 21st century is in Because of its toxicity, European and North American lead–acid batteries. The reactions in the battery be- manufacturers use alternatives such as zinc.[228][229] tween lead, lead dioxide, and provide a re- Lead glass is composed of 12–28% lead oxide, changing liable source of voltage.[r] The lead in batteries under- its optical characteristics and reducing the transmission goes no direct contact with humans, so there are fewer of .[230] Lead-based semiconductors toxicity concerns. incorporating lead– such as lead and are used in pho- acid batteries have been installed in kilowatt and meg- tovoltaic cells and infrared detectors.[231] awatt scale applications in Australia, Japan, and the United States in frequency regulation, solar smoothing and shifting, wind smoothing, and other applica- Biological effects tions.[217] These batteries have lower energy density and [232] charge-discharge efficiency than -ion batteries, Lead has no confirmed biological role. Its prevalence [s] but are significantly cheaper.[218] in the human body—at an adult average of 120 mg — is nevertheless exceeded only by zinc (2500 mg) and Lead is used in high voltage power cables as sheathing iron (4000 mg) among the .[234] Lead salts material to prevent water diffusion into insulation; this are very efficiently absorbed by the body.[235] A small [219] use is decreasing as lead is being phased out. Its use amount of lead (1%) is stored in bones; the rest is ex- in for electronics is also being phased out by creted in and feces within a few weeks of expo- some countries to reduce the amount of environmen- sure. Only about a third of lead is excreted by a child.[236] [220] tally hazardous waste. Lead is one of three metals Continual exposure may result in the used in the Oddy test for museum materials, helping of lead.[236] detect organic acids, aldehydes, and acidic [221][222] gases. Toxicity Lead is a highly poisonous metal (whether inhaled or swallowed), affecting almost every organ and system in the human body.[237] At airborne levels of 100 mg/m3, it

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is immediately dangerous to life and health.[238] Most ingested lead is absorbed into the blood- stream.[239] The primary cause of its toxicity is its predilection for interfering with the proper func- tioning of enzymes. It does so by binding to the sulfhydryl groups found on many enzymes,[240] or mimicking and displacing other metals which act as cofactors in many enzymatic reactions.[241] Among the essential metals that lead interacts with are calcium, iron, and zinc.[242] High levels of calcium and iron tend to provide some protec- tion from lead poisoning; low levels cause in- creased susceptibility.[235]

Effects Lead can cause severe damage to the brain and kidneys and, ultimately, death. By mimicking calcium, lead can cross the blood-brain barrier. It degrades the sheaths of , re- duces their numbers, interferes with neurotrans- mission routes, and decreases neuronal growth.[240] In the human body, lead inhibits por- phobilinogen synthase and , pre- venting both formation and the incorporation of iron into protoporphyrin IX, the final step in synthesis. This causes in- effective heme synthesis and microcytic ane- mia.[243] Symptoms of lead poisoning include nephropa- thy, colic-like abdominal pains, and possibly weakness in the fingers, wrists, or ankles. Small blood pressure increases, particularly in middle- aged and older people, may be apparent and can Figure 19 | Symptoms of lead poisoning cause . Several studies, mostly cross-sec- Mikael Häggström, public domain tional, found an association between increased lead exposure and decreased heart rate variabil- [244] ity. In pregnant women, high levels of exposure to Exposure sources lead may cause . Chronic, high-level expo- sure has been shown to reduce fertility in males.[245] Lead exposure is a global issue since lead mining and smelting, and battery manufacturing/disposal/recy- In a child's developing brain, lead interferes with syn- cling, are common in many countries. Lead enters the apse formation in the , neurochemical body via inhalation, ingestion, or skin absorption. Al- development (including that of ), and [246] most all inhaled lead is absorbed into the body; for in- the organization of ion channels. Early childhood ex- gestion, the rate is 20–70%, with children absorbing a posure has been linked with an increased risk of sleep higher percentage than adults.[250] disturbances and excessive daytime sleepiness in later childhood.[247] High blood levels are associated with de- Poisoning typically results from ingestion of food or wa- layed puberty in girls.[248] The rise and fall in exposure to ter contaminated with lead, and less commonly after airborne lead from the combustion of tetraethyl lead in accidental ingestion of contaminated soil, dust, or lead- gasoline during the 20th century has been linked with based paint.[251] Seawater products can contain lead if historical increases and decreases in crime levels, a hy- affected by nearby industrial .[252] Fruit and veg- pothesis which is not universally accepted.[249] etables can be contaminated by high levels of lead in the they were grown in. Soil can be contaminated

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the calcium chelate of the disodium salt of ethylenedia- minetetraacetic acid (EDTA). It has a greater affinity for lead than calcium, with the result that lead chelate is formed by exchange and excreted in the urine, leaving behind harmless calcium.[262]

Environmental effects The extraction, production, use, and disposal of lead and its products have caused significant contamination of the Earth's soils and waters. Atmospheric emissions of lead were at their peak during the Industrial Revolu- Figure 20 | Battery collection site in Dakar, Senegal, where at least 18 children died of lead poisoning in 2008 tion, and the leaded gasoline period in the second half J Caravanos, CC-BY-SA 4.0 of the twentieth century. Lead releases originate from natural sources (i.e., concentration of the naturally oc- through particulate accumulation from lead in pipes, curring lead), industrial production, incineration and re- , and residual emissions from leaded gaso- cycling, and mobilization of previously buried lead.[263] line.[253] Elevated concentrations of lead persist in soils and sed- The use of lead for water pipes is problematic in areas iments in post-industrial and urban areas; industrial with soft or acidic water.[254] forms insoluble emissions, including those arising from coal burn- [264] layers in the pipes whereas soft and acidic water dis- ing, continue in many parts of the world, particularly [265] solves the lead pipes.[255] Dissolved in in the developing countries. the carried water may result in the formation of soluble Lead can accumulate in soils, especially those with a lead ; oxygenated water may similarly dis- high organic content, where it remains for hundreds to solve lead as lead(II) hydroxide.[256] Drinking such water, thousands of years. Environmental lead can compete over time, can cause health problems due to the toxicity with other metals found in and on plants surfaces po- of the dissolved lead. The harder the water the more tentially inhibiting and at high enough and sulfate it will contain, and the concentrations, negatively affecting plant growth and more the inside of the pipes will be coated with a pro- survival. Contamination of soils and plants can allow tective layer of or lead sulfate.[257] lead to ascend the food chain affecting Ingestion of applied lead-based paint is the major and animals. In animals, lead exhibits toxicity in many source of exposure for children: a direct source is chew- organs, damaging the nervous, renal, reproductive, ing on old painted window sills. Alternatively, as the ap- hematopoietic, and cardiovascular systems after inges- [266] plied dry paint deteriorates, it peels, is pulverized into tion, inhalation, or skin absorption. Fish uptake lead [267] dust, and then enters the body through hand-to-mouth from both water and sediment; bioaccumulation in contact or contaminated food, water, or alcohol. In- the food chain poses a hazard to fish, birds, and [268] gesting certain home remedies may result in exposure mammals. to lead or its compounds.[258] Antropogenic lead includes lead from shot and sinkers. Inhalation is the second major exposure pathway, af- These are among the most potent sources of lead con- [269] fecting smokers and especially workers in lead-related tamination along with lead production sites. Lead occupations.[239] Cigarette contains, among was banned for shot and sinkers in the United States in [270] other toxic substances, radioactive lead-210.[259] 2017, although that ban was only effective for a month,[271] and a similar ban is being considered in the Skin exposure may be significant for people working European Union.[272] with organic lead compounds. The rate of skin absorp- tion is lower for inorganic lead.[260] Analytical methods for the determination of lead in the environment include , X-ray fluores- Treatment cence, atomic spectroscopy and electrochemical meth- ods. A specific ion-selective electrode has been devel- Treatment for lead poisoning normally involves the ad- oped based on the S,S'-methylenebis(N,N- ministration of and succimer.[261] Acute diisobutyldithiocarbamate).[273] An important bi- cases may require the use of disodium calcium edetate, omarker assay for lead poisoning is δ-aminolevulinic acid levels in plasma, serum, and urine.[274]

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but specialized uses of other pig- NFPA 704 ments such as yellow lead chromate fire diamond remain.[168] Stripping old paint by sanding produces dust which can be inhaled.[281] Lead abatement pro- grams have been mandated by some authorities in properties where young [282] children live. Figure 22 | Lead waste, depending of the juris- Fire diamond for lead granules diction and the nature of the waste,

may be treated as household waste (in order to facili- tate lead abatement activities),[283] or potentially haz- ardous waste requiring specialized treatment or stor- age.[284] Lead is released to the wildlife in shooting places and a number of lead management practices, such as stewardship of the environment and reduced public scrutiny, have been developed to counter the lead contamination.[285] Lead migration can be en- hanced in acidic soils; to counter that, it is advised soils be treated with lime to neutralize the soils and prevent leaching of lead.[286]

Figure 21 | of a swan found dead in Conde-sur- Research has been conducted on how to remove lead l'Escaut (northern ), highlighting lead shot. There are from biosystems by biological means: Fish bones are hundreds of lead pellets; a dozen is enough to kill an adult being researched for their ability to bioremediate lead swan within a few days. Such bodies are sources of environ- in contaminated soil.[287][288] The fungus Aspergillus ver- mental contamination by lead. sicoloris effective at removing lead ions.[289] Several Rafael Mateo, CC-BY-SA 3.0 bacteria have been researched for their ability to re- move lead from the environment, including the sulfate- reducing bacteria Desulfovibrio and Desulfotomaculum, Restriction and remediation both of which are highly effective in aqueous solu- [290] By the mid-1980s, there was significant decline in the tions. use of lead in industry. In the United States, environ- mental regulations reduced or eliminated the use of lead in non-battery products, including gasoline, paints, Acknowledgements solders, and water systems. Particulate control devices I would like to thank the many Wikipedia editors who were installed in coal-fired power plants to capture lead commented on, copyedited, contributed to, or other- [264] emissions. Lead use was further curtailed by the Eu- wise helped to improve this article, including those who ropean Union's 2003 Restriction of Hazardous Sub- assisted at the Wikipedia featured article candidacy: [275] stances Directive. A large drop in lead deposition oc- Graeme Bartlett, Jimfbleak, Sandbh, Nergaal, DePiep, curred in the Netherlands after the 1993 national ban on John, Cas Liber, Axl, Double sharp, Smurrayinchester, use of lead shot for hunting and sport shooting: from edwininlondon, and Parcly Taxel. I would also like to [276] 230 tonnes in 1990 to 47.5 tonnes in 1995. thank the reviewers who provided journal peer reviews: In the United States, the permissible exposure limit for Marshall Sumter, Jaclyn Catalano, an anonymous re- lead in the workplace, comprising metallic lead, inor- viewer, and Robert M. Gogal Jr. ganic lead compounds, and lead soaps, was set at 50 μg/m3 over an 8-hour workday, and the limit at 5 μg per 100 g of blood in 2012.[277] Lead may still Notes [278] be found in harmful quantities in stoneware, vi- a. About 10% of the lanthanide contraction has been attributed to relativistic nyl[279] (such as that used for tubing and the insulation effects.[2] [t] b. The tetrahedral allotrope of tin is called α- or gray tin and is stable only at of electrical cords), and Chinese brass. Old houses or below 13.2 °C (55.8 °F). The stable form of tin above this temperature is may still contain lead paint.[279] White lead paint has called β- or white tin and has a distorted face centered cubic (tetragonal) structure which can be derived by compressing the tetrahedra of gray tin been withdrawn from sale in industrialized countries, along their cubic axes. White tin effectively has a structure intermediate

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between the regular tetrahedral structure of gray tin, and the regular face 17. Brenner 2003, p. 396. centered cubic structure of lead, consistent with the general trend of 18. Jones 2014, p. 42. increasing metallic character going down any representative group.[8] 19. Lide 2005, pp. 4-13, 4-21, 4-33. c. A quasicrystalline thin-film allotrope of lead, with pentagonal symmetry, 20. Vogel & Achilles 2013, p. 8. was reported in 2013. The allotrope was obtained by depositing lead atoms 21. Anderson 1869, pp. 341–43. on the surface of an icosahedral silver-- . Its 22. Gale & Totemeier 2003, pp. 15–2–15–3. conductivity was not recorded.[9][10] 23. Thornton, Rautiu & Brush 2001, p. 8. d. Diamond cubic structures with lattice parameters around the lattice 24. Lide 2005, p. 12-219. parameter of silicon exists both in thin lead and tin films, and in massive 25. Willey 1999. lead and tin, freshly solidified in vacuum of ≈5 x 10-6 Torr. Experimental 26. Lide 2005, p. 12-45. evidence for almost identical structures of at least three oxide types is 27. Blakemore 1985, p. 272. presented, demonstrating that lead and tin behave like silicon not only in 28. Webb, Marsiglio & Hirsch 2015. the initial stages of crystallization, but also in the initial stages of 29. IAEA - Nuclear Data Section 2017. oxidation.[11] 30. University of Nuclear Forensic Search Project. e. Malleability describes how easily it deforms under compression, whereas 31. Stone 1997. ductility means its ability to stretch. 32. Marcillac et al. 2003, pp. 876–78. f. : to go down like a lead balloon. 33. World Nuclear Association 2015. g. A (wet) finger can be dipped into molten lead without risk of a burning 34. Beeman et al. 2013. injury.[25] 35. Committee on Evaluation of EPA Guidelines for Exposure to Naturally h. An even number of either or neutrons generally increases the Occurring Radioactive Materials et al. 1999, pp. 26, 30–32. nuclear stability of isotopes, compared to isotopes with odd numbers. No 36. Smirnov, Borisevich & Sulaberidze 2012. elements with odd atomic numbers have more than two stable isotopes; 37. Greenwood & Earnshaw 1998, p. 368. even-numbered elements have multiple stable isotopes, with tin (element 38. Levin 2009, pp. 40–41. 50) having the highest number of isotopes of all elements, ten.[29]See Even 39. Webb 2000, p. 115. and odd atomic nuclei for more details. 40. Wrackmeyer & Horchler 1990. i. The half-life found in the experiment was 1.9×1019 years.[32]A kilogram of 41. Cangelosi & Pecoraro 2015. natural bismuth would have an activity value of approximately 0.003 42. Fiorini 2010, pp. 7–8. (decays per second). For comparison, the activity value of 43. Takahashi et al. 1987. natural radiation in the human body is around 65 becquerels per kilogram 44. 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